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Terahertz Time-Domain Spectroscopy and Visualization of Biological Objects
Nedvědová, Marie ; Kužel,, Petr (referee) ; Vrba, Jan (referee) ; Provazník, Ivo (advisor)
This thesis deals with the methods of Terahertz (THz) spectroscopy to observe the kinetics of haemostatic materials used for supporting the native mechanism of haemostasis. The theoretical part follows the physical principles of THz time-domain spectroscopy (THz TDS), mentions the advantages and limitations of this method and its application possibilities for the characterization of biomedical materials. Further, there are specified properties of actual haemostats, described principles of their function and usage in practice, including their interaction with the living tissue. There were performed experiments monitoring the kinetics of physiologic reaction of the tissue adhesive based on the cyanoacrylates and absorbable haemostats. The mechanisms of monitored reactions were explained based on the physical-chemical principles that are used also for the kinetic models’ derivation. Modelling of the measured data results in the estimation of the parameters characterizing the observed samples. The most interesting parameter is the time constant of the reaction because of the possibility to compare reaction rates of different types of haemostats. The detailed analysis of this parameter is performed using the means of statistical methods. Tissue adhesive samples were measured by other spectroscopic and microscopic methods to compare the findings with the experimental results of the THz TDS. Data were processed using algorithms designed especially for this experiment and analysed using mathematical methods.
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synthesis of conjugated polyacetylene based polymers
Duchoslavová, Zuzana ; Zedník, Jiří (advisor) ; Doubský, Jan (referee)
Mostly new acetylene based monomers were prepared. All monomers were prepared by the means of standard spectroscopic methods. All monomers were successfully polymerized using standard metathesis TaCl5 based catalyst. Prepared polymers were characterized by the means of GPC/GPC-MALLS chromatography and standard spectral methods. Fluorescence properties of all prepared compounds were also studied: quantum fluorescence yields were determined and excitation and emission fluorescence spectra were recorded. Polymerization on modern metathesis Grubbs-Hoveyda catalytic systems of all prepared monomers was also tested. These reactions were only partially successful and only low molecular weight oligomers in mediocre yields were obtained.
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Preparation and polymerization ethynyl pyridine based monomers
Faukner, Tomáš ; Zedník, Jiří (advisor) ; Hoškovec, Michal (referee)
A group of monomers based on disubstitued ethynylpyridine (3-PyCCPh-4-t-Bu, 2-PyCCR, R = 4-t-BuPh, 2-Py, n-Bu) and 4-tert-butyphenylethynyl (4-t-BuPhCCPh-p-OR, R = SiPh2-t-Bu, Si-i-Pr3) were prepared by Sonogashira cross-coupling reaction (PdCl2[(PPh3]2/CuI). All of these monomers were charakterized by IR, UV/vis and NMR spectroscopy. Ethynylpyridine based monomers were polymerised by quarternization (ethylbromid was used as a quarternization agent) and by Grubbs-Hoveyda 2nd generation catalyst. As a product of the quarternization were obtained oligomers compounded by 2 - 13 monomers units (Mw: 1600 - 6000, Y 70%). Only low molecular weight oligomers were also obtained by Grubbs-Hoveyda 2nd generation polymerization (Mw: 400 - 1500, Y 34 %). Monomers based on 4-tert-butyphenylethynyl were polymerized by TaCl5/Bu4Sn/Toluen catalytic system. In that case were obatined polymers (Mw: 64 000 - 200 000, IP = 2,3 -3,9, Y 75 %). Products of polymeryzations were charakterized by GPC, IR, UV/vis and NMR spectroscopy.
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Study of molecular weight and configurational stability of substituted polyacetylenes
Trhlíková, Olga ; Sedláček, Jan (advisor) ; Netopilík, Miloš (referee) ; Žigon, Majda (referee)
3 ABSTRACT Complexes [Rh(cycloolefin)(acac)] (cycloolefin = norborna-2,5-diene, cycloocta- 1,5-diene and cyclooctatetraene) were investigated as catalysts of polymerization of monosubstituted acetylenes into stereoregular cis-transoid polyacetylenes. All complexes were highly active in arylacetylenes polymerizations in both coordinating and non-coordinating solvents. Selection of solvent and cycloolefin ligand of the catalyst allowed the control over polymer MW. The onset of initiation in the [Rh(cycloolefin)(acac)]/monomer systems proceeded as the proton transfer from the monomer molecule to the acac ligand under the release of acetylacetone and coordination of -C≡CR ligand to Rh(cycloolefin) moiety. Cis-transoid poly(phenylacetylene) and poly[(2,4-difluorophenyl)acetylene]s with required initial MW were prepared with these catalysts and submitted to the long-term ageing in which the polymers were exposed to the atmosphere and diffuse daylight either dissolved in tetrahydrofuran or in the solid state. Tightly connected processes of cis-to-trans isomerization of the polymer main-chains double bonds and oxidative degradation were found to proceed during polymers ageing in the solution. Besides, the formation of corresponding cyclotrimers accompanied the polymers ageing. However, the cyclotrimers amount was...
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Terahertz Time-Domain Spectroscopy and Visualization of Biological Objects
Nedvědová, Marie ; Kužel,, Petr (referee) ; Vrba, Jan (referee) ; Provazník, Ivo (advisor)
This thesis deals with the methods of Terahertz (THz) spectroscopy to observe the kinetics of haemostatic materials used for supporting the native mechanism of haemostasis. The theoretical part follows the physical principles of THz time-domain spectroscopy (THz TDS), mentions the advantages and limitations of this method and its application possibilities for the characterization of biomedical materials. Further, there are specified properties of actual haemostats, described principles of their function and usage in practice, including their interaction with the living tissue. There were performed experiments monitoring the kinetics of physiologic reaction of the tissue adhesive based on the cyanoacrylates and absorbable haemostats. The mechanisms of monitored reactions were explained based on the physical-chemical principles that are used also for the kinetic models’ derivation. Modelling of the measured data results in the estimation of the parameters characterizing the observed samples. The most interesting parameter is the time constant of the reaction because of the possibility to compare reaction rates of different types of haemostats. The detailed analysis of this parameter is performed using the means of statistical methods. Tissue adhesive samples were measured by other spectroscopic and microscopic methods to compare the findings with the experimental results of the THz TDS. Data were processed using algorithms designed especially for this experiment and analysed using mathematical methods.
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Study of molecular weight and configurational stability of substituted polyacetylenes
Trhlíková, Olga
Complexes [Rh(cycloolefin)(acac)] (cycloolefin = norborna-2,5-diene, cycloocta- 1,5-diene and cyclooctatetraene) were investigated as catalysts of polymerization of monosubstituted acetylenes into stereoregular cis-transoid polyacetylenes. All complexes were highly active in arylacetylenes polymerizations in both coordinating and non-coordinating solvents. Selection of solvent and cycloolefin ligand of the catalyst allowed the control over polymer MW. The onset of initiation in the [Rh(cycloolefin)(acac)]/monomer systems proceeded as the proton transfer from the monomer molecule to the acac ligand under the release of acetylacetone and coordination of -C≡CR ligand to Rh(cycloolefin) moiety. Cis-transoid poly(phenylacetylene) and poly[(2,4-difluorophenyl)acetylene]s with required initial MW were prepared with these catalysts and submitted to the long-term ageing in which the polymers were exposed to the atmosphere and diffuse daylight either dissolved in tetrahydrofuran or in the solid state. Tightly connected processes of cis-to-trans isomerization of the polymer main-chains double bonds and oxidative degradation were found to proceed during polymers ageing in the solution. Besides, the formation of corresponding cyclotrimers accompanied the polymers ageing. However, the cyclotrimers amount was too...
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Polycyclotrimerization of alkynes with internal ethynyl groups
Sokol, Jiří ; Sedláček, Jan (advisor) ; Balcar, Hynek (referee)
The diynes of both aliphatic and aromatic types comprising either (i) two internal ethynyl groups or (ii) one internal and one terminal ethynyl group in the molecule were revealed as appropriate monomers for the Co2(CO)8 catalyzed polycyclotrimerization yielding high-molecular-weight products. The polycyclotrimerization of aliphatic diynes with a short (CH2)2 link between ethynyl groups and the polycyclotrimerization of aromatic diynes provided polycyclotrimer networks with tri-, tetra-, penta- and hexasubstituted benzene segments. The polycyclotrimers of aliphatic diynes did not exhibit microporous texture. On the other side, the polycyclotrimers of aromatic monomers were mostly microporous with specific surface area up to SBET = 499 m2 /g. The nitrogen desorption isotherms on microporous polycyclotrimers exhibited a significant unclosed hysteresis. This indicated that the penetration of nitrogen into polymers was accompanied by formation of temporary pores or opening permanent pores of worse accessibility.
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Study of molecular weight and configurational stability of substituted polyacetylenes
Trhlíková, Olga ; Sedláček, Jan (advisor) ; Netopilík, Miloš (referee) ; Žigon, Majda (referee)
3 ABSTRACT Complexes [Rh(cycloolefin)(acac)] (cycloolefin = norborna-2,5-diene, cycloocta- 1,5-diene and cyclooctatetraene) were investigated as catalysts of polymerization of monosubstituted acetylenes into stereoregular cis-transoid polyacetylenes. All complexes were highly active in arylacetylenes polymerizations in both coordinating and non-coordinating solvents. Selection of solvent and cycloolefin ligand of the catalyst allowed the control over polymer MW. The onset of initiation in the [Rh(cycloolefin)(acac)]/monomer systems proceeded as the proton transfer from the monomer molecule to the acac ligand under the release of acetylacetone and coordination of -C≡CR ligand to Rh(cycloolefin) moiety. Cis-transoid poly(phenylacetylene) and poly[(2,4-difluorophenyl)acetylene]s with required initial MW were prepared with these catalysts and submitted to the long-term ageing in which the polymers were exposed to the atmosphere and diffuse daylight either dissolved in tetrahydrofuran or in the solid state. Tightly connected processes of cis-to-trans isomerization of the polymer main-chains double bonds and oxidative degradation were found to proceed during polymers ageing in the solution. Besides, the formation of corresponding cyclotrimers accompanied the polymers ageing. However, the cyclotrimers amount was...
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Study of molecular weight and configurational stability of substituted polyacetylenes
Trhlíková, Olga
Complexes [Rh(cycloolefin)(acac)] (cycloolefin = norborna-2,5-diene, cycloocta- 1,5-diene and cyclooctatetraene) were investigated as catalysts of polymerization of monosubstituted acetylenes into stereoregular cis-transoid polyacetylenes. All complexes were highly active in arylacetylenes polymerizations in both coordinating and non-coordinating solvents. Selection of solvent and cycloolefin ligand of the catalyst allowed the control over polymer MW. The onset of initiation in the [Rh(cycloolefin)(acac)]/monomer systems proceeded as the proton transfer from the monomer molecule to the acac ligand under the release of acetylacetone and coordination of -C≡CR ligand to Rh(cycloolefin) moiety. Cis-transoid poly(phenylacetylene) and poly[(2,4-difluorophenyl)acetylene]s with required initial MW were prepared with these catalysts and submitted to the long-term ageing in which the polymers were exposed to the atmosphere and diffuse daylight either dissolved in tetrahydrofuran or in the solid state. Tightly connected processes of cis-to-trans isomerization of the polymer main-chains double bonds and oxidative degradation were found to proceed during polymers ageing in the solution. Besides, the formation of corresponding cyclotrimers accompanied the polymers ageing. However, the cyclotrimers amount was too...
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